Anthraquinone derivatives



United States Patent ANTHRAQUINONE DERIVATIVES Frank Lodge, Blackley, Manchester, England, 'assignor to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application December 12, 1952 Serial No. 325,695

Claims priority, application Great Britain December 21, 1951 7 Claims. (Cl. 260-380) This invention relates to the manufacture of new anthraquinone derivatives and more particularly it relates to anthraquinone dyestuffs useful for dyeing cellulose acetate rayon.

According to my invention I provide new anthraquinone derivatives of the general formula:

X 0 ll I OH I l V (EHz-O-(CHiCHzOLZ wherein Y, Z and n have the meaning stated above.

As suitable 1-hydroxy-4-nitro-anthraquinones for use in the process of this invention there may be mentioned for example 1:5 dihydroxy-4:8-dinitroanthraquinone, 1:5 :8-trihydroxy-4-nitro-anthraquinone and 1:8-dihydroxy-4 -dinitro-anthraquinone.

Suitable primary amines which may be used in the process of the invention include for example m-arninobenzyl fl-hydroxyethyl ether, m-aminobenzyl B-(fY-hydroxyethoxy) -ethyl ether, S-amino-Z-methylbenzyl p345- hydroxyethoxy) -ethyl ether, m-aminobenzyl B-(fi'-hydroxyethoxyethoxy)-ethyl ether, m-aminobenzyl B-hydroxypropyl ether, m-aminobenzyl gamma-hydroxypropyl ether and m-aminobenzyl ,S-methoxyethyl ether.

The reaction between the substituted anthraquinone and the primary arylamine may be conveniently brought about by heating the reactants together, the amine being conveniently in excess and the reaction temperature being preferably between 100 C.-130 C. The reaction may also be carried out in the presence of an organic solvent such as for example fl-ethoxyethanol.

The new anthraquinone dyestuffs of this invention have very good aflinity for acetate rayon to which they impart a blue colour which is fast to light and has a high resistance to the action of combustion products of coal gas. The new dyestuffs either singly or in the form of mixtures are also valuable for colouring polyester fibres.

The following examples, in which the parts are by weight, illustrate but do not limit the invention:

2,933,508 Patented. P 19, 9,

2 Example 1 10 parts of 1:8-dihydroxy-4:S-dinitroanthraquinone are stirred with 40 parts of m-aminobenzyl B-(B-hydroxyethoxy)-ethyl etherand heated under a reflux condenser at 120 C. during 3 hours. The mixture is cooled to 50 C. and poured into a mixture of 400 parts of ethanol and 100 parts of water. The mixture is allowed to stand for 2 hours and it is then filtered and the solid residue on the filter is washed with 70% ethanol. The product is a new dyestuff which in aqueous dispersion colours acetate rayon in strong, attractive blue shades possessing very good fastness to burnt-gas fumes and to light.

Example 2 5 parts of 1:5-dihydroxy-4:8 dinitroanthraquinone are mixed with 20 parts of m-aminobenzyl fi-hydroxyethyl ether. The mixture is stirred and heated under a reflux condenser at 120 C. during 2 hours. The product is isolated as described in Example 1. The product is a new dyestufi which in aqueous dispersion colours acetate rayon giving strong blue shades of very good fastness to light and burnt-gas fumes.

Example 3 10 parts of 1:8-dihydroxy-4:S-dinitro-anthraquinone, 30 parts of p-ethoxyethanol and 10 parts of m-aminobenzyl fl-(fl'hydroxyethoxy)-ethyl ether are stirred 'together under a reflux condenser at 130 C.-l35 C. for 18 hours. The mixture is cooled to C., 30 parts of ethanol are added and the mixture is filtered to re! move unchanged starting material. The blue solution; so obtained is diluted with parts of ethanol and parts of water are then added slowly to precipitate the Example 4 5 parts of 1:5 :8-trihydroxy-4-nitroanthraquinone, 10 parts of p-ethoxyethanol and 5 parts of m-aminobenzyl fl-(fi'-hydroxyethoxy)-ethyl ether are stirred together at 170-175 for 18 hours. The mixture is cooled and diluted with ethanol and the precipitated dyestufi is filtered 01f and washed with ethanol. When dispersed in water the new product dyes acetate rayon in reddish blue shades of very good fastness tov burnt-gas fumes and to light.

Example 5 20 parts of 1:8-dihydroxy-4:S-dinitroanthraquinone, 40 parts of m-aminobenzyl B-hydroxypropyl ether and 40 parts of phenol are stirred together. at 125 C. for 16, hours. The deep blue solution is cooled and diluted with 200 parts of fi-ethoxyethanol and 380 parts of ethanol. parts of water are then added. The mixture is allowed to stand and the new dyestufi which crystallizes out,.-is filtered ofi, washed with 70% ethanol and dried. When. dispersed in water the product yields deep blue dyeings.

Y on acetate rayon possessing very good fastness to burnt-' gas fumes and to light.

I Example 6 i In place of the 20 parts of 1:8-dihydroxy-4:5-dinitroanthraquinone used in Example 5 there are used 20 parts.

u es nd to light.

' o l=r5 dih roxr -d n i epthxa a aane .Ihe preduct gives blue shades on acetate of similar properties to those obtained with the dyestuffs of Example 5.

Example 7 10 parts of'the dyestufi of Example-5 and 10 parts of i the dyestuff of Example 6 are rnixed'together and added gradually, to 200 parts of 70% sulphuric acid which is stirred at 10-15 C. The mixture is stirred for half an hour and then poured on to 1,000 parts of a mixture of ice and water. The precipitated dyestuff is filtered off, washed acid-free with water and milled to give a fine dispersion. The afiinity of the product for acetate rayon is very good and bright, deep-blue shades are obtained possessing very good fastness to burnt-gas fumes and to light. The product is valuable for use in colouring polyethylene terephthalate textile materials.

Example 8 6 parts of 1= ih a n mhr qu n ne.' 12 parts of phenol and 12 parts of mfaminobenz yl gammahydtoxypropyl ether are stirred together at 125 C. for h 'r parts o fiae hqry th eql re ad d and t b 'e e Q t n d s QQQEQ t9 80 C- h d s ijitis pr pi e b flins .0 P rts of et an ens! then 50 parts of Water to the solution, The mixture allowed to stand at 20 C. for 2 hours and the'dyestufi is filtered ofl, washed with ethanol and milled to form a dispersed paste. Thedyestufi dyes rayon in bright, deepblue shades possessing very good fastness to burnt-gas Example 9 10 parts of 1:8-dihydroxy-4:S-dinitro-anthraquinone, 20 parts of phenol and 20 parts of m-aminobenzyl e hydroxyethyl ether are stirred together at 125 C. for 18 flhtmrs. 'The mixture is cooled to 80 C. and 200 parts of ethanol are. added. The mixture is allowed to cool and the a new dyestuif which cystallizes out is filtered off, washed withethanol and dried. When dispersed in water the product yields attractive blue shades on acetate rayon of very good fastness to gas fumes and to light.

Example 10 t parts of the dyestuff of Example 8 and 5 parts of the dyestufl of Example 9 are mixed together and added gradually to 100 parts of 70% sulphuric acid which is stirred at -15 C. The mixture is stirred for about minutes to dissolve the dyestutf and the acid mixture.

is then poured into 500 parts of a mixture of ice and water. The precipitated dyestuif is filtered oil and washed acid-free and finally milled in the'presence of a dispersing agent. The dyestuff mixture thus obtained has very good afiinity for acetate rayon which it dyes in attractive blue shades of very good fastness to burnt-gas fumes and to light.

Example 11 6 parts of 1:8-dihydroxy-4:5-dinitro anthraquinone, 12 parts of phenol and 12 parts of S-amino-Z-methyl-benzyl fl-(fi'-hydroxyethoxy)-ethyl ether are stirred together at 125 C. for 16 hours. The dyestuff is isolated in a manner similar to that used in Example 8. It dyes acetate" rayon in blue shades possessing 7 very good properties of fastness to burnt-gas fumes.

Example 12 8 parts of 1:5-dihydroxy-4:S-dinitro-anthraquinone, 16 parts of phenol and 16 parts of m-aminobenzyl fl-methoxyethyl other are stirred together at 125 C. for 18 hours. After cooling to 50 C. 80 parts of B-ethoxyethanol and 1 20 parts of ethanol are added and the mixtureso obtained is allowed to stand for 12 hours. The solid product which crystallizes out is then filtered ofi,

washed with ethanol anddried to give a dark blue powder which when dispersed in water dyes acetate rayon in attract v b ue s ades o ery good ,ia mess to burnt-se fumes and to light.

What I claim is:

1. Anthraquinone derivatives having a formula selected from the group consisting of and I H I crat 65110.03

wherein one X stands for N0 and the other X stands for OH, Y is selected from the group consisting of hydrogen and methyl, and n has a value of 1 to 3.

3. The compound of the formula II I 03.0 CH2CH20H H NH' 4. The compound of the formula OHO OH lll l cmoomomo omomon NO: (I) NH 5. The anthraquinone derivative of the following .for-f mula; f

6. The anthraquinone derivative of the following for- 7. The anthraquinone derivative of the following formula: m

0H 0 0H om 0 on I H I If 5 7 N0: 0 1 111 OH 0 NH 10 CHr-O-CHz-CH2-CH7OH CHPO CH' CI; GHZ References Cited in the file of this patent UNITED STATES PATENTS 15 2,480,269 Seymour et a1 Aug. 30, 1949 2,585,681 Randall et al. Feb. 12, 1952 2,641,602 Straley et a1. June 9, 1953 2,651,641 Straley et a1. Sept. 8, 1953 

1. ANTHRAQUINONE DERIVATIVES HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF 